EP1035229B1 - Rhodium bath and process for rhodium deposition - Google Patents
Rhodium bath and process for rhodium deposition Download PDFInfo
- Publication number
- EP1035229B1 EP1035229B1 EP20000103134 EP00103134A EP1035229B1 EP 1035229 B1 EP1035229 B1 EP 1035229B1 EP 20000103134 EP20000103134 EP 20000103134 EP 00103134 A EP00103134 A EP 00103134A EP 1035229 B1 EP1035229 B1 EP 1035229B1
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- EP
- European Patent Office
- Prior art keywords
- rhodium
- bath
- water
- deposition
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
Definitions
- the invention relates to a rhodium bath and a method for depositing rhodium on a substrate, in particular for the electroless rhodium plating of surfaces, according to the preamble of the main claims.
- electroless metallization processes or metallization baths are used in particular for the coating of nonconductive surfaces, of powders or of components or substrates which can not be contacted individually or only at great expense.
- Known rhodium baths also preferably use chlorine-containing rhodium starting compounds, which often lead to disturbances in applications in sensor technology.
- the rhodium bath according to the invention and the method of depositing it according to claims 1 and 5 have the advantage over the prior art that the bath yield is substantially increased and only a very small part of the rhodium used precipitates or precipitates on the vessel wall. Typical Badausbeuten are about 90% and above.
- substrates such as non-conductive surfaces, metals, powders or other difficult to access or difficult to contact components in a simple, reliable and cost-effective manner.
- the rhodium bath according to the invention is almost universally applicable to a wide variety of substrates and, moreover, insensitive to fluctuations in the bath parameters with regard to the pH of the bath, the bath temperature and the concentrations of the individual bath constituents used.
- a further significant advantage is that water can be used as the solvent for the rhodium bath according to the invention and the rhodium compounds used are readily soluble in water.
- the thickness of the deposition and the deposition rate reach the substrate used.
- the pH of the rhodium bath is adjusted to a value of 8.5 to 10.5 and more preferably 9 to 10.
- the bath temperature is advantageously a temperature of 70 ° C to 95 ° C, preferably from 80 ° C to 90 ° C.
- a wetting agent in particular a surfactant such as a fluoroalcohol, is advantageously added to the rhodium bath for better wetting of a submerged substrate.
- a reducing agent in particular a 10% hydrazine solution.
- rhodium bath is first as a good water-soluble rhodium compound ammonium di (pyridine-2,6-dicarboxylate) rhodium (III), or a rhodium acetate h.
- ammonium di pyridine-2,6-dicarboxylate
- rhodium (III) rhodium (III)
- rhodium acetate h rhodium acetate h.
- the compound [Rh 3 O (CH 3 COO) 6 (H 2 O) 3 ] (CH 3 COO) dissolved in water as a solvent a combination of several of the above well water-soluble rhodium compounds is possible.
- Rhodium compounds which are readily soluble in water are understood to mean those rhodium compounds which dissolve in water at a temperature of from 80 ° C. to 90 ° C. in an amount of at least 1 g / l without precipitating or spontaneously reducing.
- Preferred rhodium compounds which are readily soluble in water are those rhodium compounds which can be dissolved in water at said temperatures in an amount of typically at least 10 g / l without precipitation or spontaneous reduction.
- the upper limit of the amount of rhodium dissolved or dissolved in water is approximately 50 g / l in the cases relevant to the invention.
- the amount of the rhodium compound to be dissolved in the individual case in the water depends on the size of the surface to be metallized or coated or on the surface to be achieved Thickness of the coating and can therefore be easily calculated by the expert in the specific case thereof.
- a surfactant such as, for example, a fluoroalcohol in a concentration of 0.01% is further added to the rhodium bath produced.
- the temperature of the rhodium bath is 70 ° C to 95 ° C, preferably 80 ° C to 90 ° C.
- the pH of the bath is adjusted to a value of 8.5 to 10.5, preferably 9 to 10.
- the adjustment of the pH is carried out, for example, by means of ammonia, NaOH or KOH.
- a substrate is now introduced or immersed, on which the rhodium contained in the bath is deposited electrolessly in metallic form.
- a substrate to be metallized for example, a non-conductive ceramic powder, a ceramic substrate, a metallic powder or a metallic component, in particular Al 2 O 3 , ZrO 2 or Pt, comes into question.
- the substrate Before the substrate is inserted or immersed, the substrate can additionally be activated beforehand in a manner known per se. This happens, for example, via a deposition of a Pd salt on the surface.
Description
Die Erfindung betrifft ein Rhodiumbad und ein Verfahren zum Abscheiden von Rhodium auf einem Substrat, insbesondere zum stromlosen Rhodinieren von Oberflächen, nach der Gattung der Hauptansprüche.The invention relates to a rhodium bath and a method for depositing rhodium on a substrate, in particular for the electroless rhodium plating of surfaces, according to the preamble of the main claims.
Stromlose Metallisierungsverfahren oder Metallisierungsbäder werden, im Gegensatz zu galvanischen Verfahren, insbesondere zur Beschichtung von nichtleitenden Oberflächen, von Pulvern oder von Bauteilen oder Substraten eingesetzt, die nicht oder nur unter großem Aufwand einzeln kontaktiert werden können.In contrast to galvanic processes, electroless metallization processes or metallization baths are used in particular for the coating of nonconductive surfaces, of powders or of components or substrates which can not be contacted individually or only at great expense.
Ein Beispiel für ein derartiges Bad zum stromlosen Vergolden von Oberflächen oder Pulvern ist beispielsweise in DE 197 45 797.5 vorgeschlagen worden.An example of such a bath for electroless gold plating of surfaces or powders has been proposed for example in DE 197 45 797.5.
Ähnliche Bäder zum stromlosen Abscheiden von Rhodium sind jedoch in der Literatur bisher nur vereinzelt beschrieben. Eine Fundstelle dazu ist Molloroy & Hajdu, "Electroless Plating: Fundamentals and Applications", (1990), American Electroplaters and Surface Finishers Society. Die daraus bekannten Bäder zum stromlosen Abscheiden von metallischem Rhodium leiden jedoch an geringen Badausbeuten, d.h. das eingesetzte Rhodium wird unkontrolliert an der Gefäßwand abgeschieden oder fällt während der Metallisierung aus dem Bad aus, so daß nur wenige Prozent der eingesetzten Rhodiumverbindung zur eigentlichen Abscheidung oder Metallisierung genutzt werden und somit eine kontrollierte bzw. definierte Rhodinierung von Substraten kaum möglich ist. Überdies sind bekannte Bäder anfällig gegenüber geringen Schwankungen der Badparameter hinsichtlich Temperatur, pH-Wert und der Konzentrationen der eingesetzten Badbestandteile.However, similar baths for electroless deposition of rhodium have so far been described only sporadically in the literature. Molloroy & Hajdu, "Electroless Plating: Fundamentals and Applications", (1990), American Electroplaters and Surface Finishers Society. The known baths for electroless deposition of metallic rhodium However, they suffer from low Badausbeuten, ie the rhodium used is deposited uncontrollably on the vessel wall or precipitates during the metallization of the bath, so that only a few percent of the rhodium compound used for the actual deposition or metallization and thus a controlled or defined rhodiumation of Substrates is hardly possible. Moreover, known baths are susceptible to small variations in the bath parameters in terms of temperature, pH and the concentrations of the bath constituents used.
Bekannte Rhodiumbäder verwenden zudem bevorzugt chlorhaltige Rhodiumausgangsverbindungen, die bei Anwendungen in der Sensorik vielfach zu Störungen führen.Known rhodium baths also preferably use chlorine-containing rhodium starting compounds, which often lead to disturbances in applications in sensor technology.
Das erfindungsgemäße Rhodiumbad und das damit durchgeführte Verfahren zum Abscheiden gemäß den Ansprüchen 1 und 5 genüber dem Stand der Technik den Vorteil, daß die Badausbeute wesentlich erhöht ist und nur ein sehr geringer Teil des eingesetzten Rhodiums ausfällt oder sich an der Gefäßwand niederschlägt. Typische Badausbeuten liegen bei ca. 90% und darüber. Somit wird eine kontrollierte und definierte stromlose Abscheidung von Rhodium auf Substraten wie nichtleitenden Oberflächen, Metallen, Pulvern oder sonstigen schwer zugänglichen oder schwer zu kontaktierenden Bauteilen in einfacher Weise, zuverlässig und kostengünstig möglich.The rhodium bath according to the invention and the method of depositing it according to claims 1 and 5 have the advantage over the prior art that the bath yield is substantially increased and only a very small part of the rhodium used precipitates or precipitates on the vessel wall. Typical Badausbeuten are about 90% and above. Thus, a controlled and defined electroless deposition of rhodium on substrates such as non-conductive surfaces, metals, powders or other difficult to access or difficult to contact components in a simple, reliable and cost-effective manner.
Das erfindungsgemäße Rhodiumbad ist dabei nahezu universell auf verschiedensten Substraten einsetzbar und überdies unempfindlich gegenüber Schwankungen der Badparameter hinsichtlich des pH-Wertes des Bades, der Badtemperatur und der Konzentrationen der einzelnen eingesetzten Badbestandteile.The rhodium bath according to the invention is almost universally applicable to a wide variety of substrates and, moreover, insensitive to fluctuations in the bath parameters with regard to the pH of the bath, the bath temperature and the concentrations of the individual bath constituents used.
Ein weiterer wesentlicher Vorteil ist, daß für das erfindungsgemäße Rhodiumbad Wasser als Lösungsmittel verwendet werden kann und die eingesetzten Rhodiumverbindungen gut wasserlöslich sind.A further significant advantage is that water can be used as the solvent for the rhodium bath according to the invention and the rhodium compounds used are readily soluble in water.
Vorteilhafte Weiterbildungen der Erfindung ergeben sich aus den in den Unteransprüchen genannten Maßnahmen.Advantageous developments of the invention will become apparent from the measures mentioned in the dependent claims.
So läßt sich durch eine gezielte Einstellung der Bad- bzw. Verfahrensparameter bei der Abscheidung hinsichtlich pH-Wert, Temperatur, Konzentrationen der einzelnen Badbestandteile und Zeitpunkt, Art und Konzentration eines zugetropften Reduktionsmittels sehr vorteilhaft und einfach eine Anpassung der Abscheidung oder Metallisierung hinsichtlich der abzuscheidenden Rhodiummenge, der Dicke der Abscheidung und der Abscheidegeschwindigkeit an das eingesetzte Substrat erreichen.Thus, by a targeted adjustment of the bath or process parameters in the deposition with respect to pH, temperature, concentrations of the individual bath constituents and time, nature and concentration of a dropwise added reducing agent very easy and easy adjustment of the deposition or metallization in terms of deposited rhodium , the thickness of the deposition and the deposition rate reach the substrate used.
Besonders vorteilhaft ist weiterhin, wenn der pH-Wert des Rhodiumbades auf einen Wert von 8,5 bis 10,5 und besonders bevorzugt auf 9 bis 10 eingestellt wird. Als Badtemperatur eignet sich vorteilhaft eine Temperatur von 70°C bis 95°C, vorzugsweise von 80°C bis 90°C.Furthermore, it is particularly advantageous if the pH of the rhodium bath is adjusted to a value of 8.5 to 10.5 and more preferably 9 to 10. As the bath temperature is advantageously a temperature of 70 ° C to 95 ° C, preferably from 80 ° C to 90 ° C.
Weiterhin wird dem Rhodiumbad zur besseren Benetzung eines eingetauchten Substrates vorteilhaft ein Benetzungsmittel, insbesondere ein Tensid wie ein Fluoralkohol zugesetzt.Furthermore, a wetting agent, in particular a surfactant such as a fluoroalcohol, is advantageously added to the rhodium bath for better wetting of a submerged substrate.
Nach der Zugabe des zu metallisierenden bzw. zu rhodinierenden Substrates in das Rhodiumbad wird diesem zur Beschleunigung der stromlosen Abscheidung vorteilhaft ein Reduktionsmittel, insbesondere eine 10%-ige Hydrazinlösung zugegeben.After the addition of the substrate to be metallized or rhodinated in the rhodium bath this is advantageously added to accelerate the electroless deposition, a reducing agent, in particular a 10% hydrazine solution.
Für das Rhodiumbad wird zunächst als gut wasserlösliche Rhodiumverbindung Ammonium-di(Pyridin-2,6-dicarboxylat)-Rhodium(III), oder ein Rhodiumacetat h. beispielsweise die Verbindung [Rh3O(CH3COO)6(H2O)3](CH3COO) in Wasser als Lösungsmittel gelöst. Auch eine Kombination mehrerer der o.g. gut wasserlöslicher Rhodiumverbindungen ist möglich.For the rhodium bath is first as a good water-soluble rhodium compound ammonium di (pyridine-2,6-dicarboxylate) rhodium (III), or a rhodium acetate h. For example, the compound [Rh 3 O (CH 3 COO) 6 (H 2 O) 3 ] (CH 3 COO) dissolved in water as a solvent. A combination of several of the above well water-soluble rhodium compounds is possible.
Unter gut wasserlöslichen Rhodiumverbindungen werden dabei solche Rhodiumverbindungen verstanden, die sich bei einer Temperatur von 80°C bis 90°C in einer Menge von mindestens 1 g/l in Wasser lösen ohne auszufallen oder sich spontan zu reduzieren.Rhodium compounds which are readily soluble in water are understood to mean those rhodium compounds which dissolve in water at a temperature of from 80 ° C. to 90 ° C. in an amount of at least 1 g / l without precipitating or spontaneously reducing.
Als bevorzugte gut wasserlösliche Rhodiumverbindungen werden solche Rhodiumverbindungen eingesetzt, die sich bei den genannten Temperaturen in einer Menge von typischerweise mindestens 10 g/l in Wasser lösen lassen ohne auszufallen oder sich spontan zu reduzieren. Die Obergrenze der in Wasser gelösten oder lösbaren Rhodiummenge liegt in den für Erfindung relevanten Fällen bei ca. 50 g/l.Preferred rhodium compounds which are readily soluble in water are those rhodium compounds which can be dissolved in water at said temperatures in an amount of typically at least 10 g / l without precipitation or spontaneous reduction. The upper limit of the amount of rhodium dissolved or dissolved in water is approximately 50 g / l in the cases relevant to the invention.
Die im Einzelfall in dem Wasser zu lösende Menge der Rhodiumverbindung richtet sich nach der Größe der zu metallisierenden oder zu beschichtenden Oberfläche bzw. der zu erzielen Dicke der Beschichtung und kann daher vom Fachmann im konkreten Fall davon ausgehend leicht berechnet werden.The amount of the rhodium compound to be dissolved in the individual case in the water depends on the size of the surface to be metallized or coated or on the surface to be achieved Thickness of the coating and can therefore be easily calculated by the expert in the specific case thereof.
Zur besseren Benetzung eines im weiteren in das Rhodiumbad eingeführten Substrates wird dem hergestellten Rhodiumbad weiter ein Tensid wie beispielsweise ein Fluoralkohol in einer Konzentration von 0,01 % zugegeben.For better wetting of a substrate introduced further into the rhodium bath, a surfactant such as, for example, a fluoroalcohol in a concentration of 0.01% is further added to the rhodium bath produced.
Die Temperatur des Rhodiumbades beträgt 70°C bis 95°C, vorzugsweise 80°C bis 90°C. Der pH-Wert des Bades wird auf einen Wert von 8,5 bis 10,5, vorzugsweise von 9 bis 10 eingestellt. Die Einstellung des pH-Wertes erfolgt beispielsweise mittels Ammoniak, NaOH oder KOH.The temperature of the rhodium bath is 70 ° C to 95 ° C, preferably 80 ° C to 90 ° C. The pH of the bath is adjusted to a value of 8.5 to 10.5, preferably 9 to 10. The adjustment of the pH is carried out, for example, by means of ammonia, NaOH or KOH.
In das derart vorbereitete Rhodiumbad wird nun ein Substrat eingeführt oder eingetaucht, auf dem das in dem Bad enthaltene Rhodium in metallischer Form stromlos abgeschieden wird. Als zu metallisierendes Substrat kommt dazu beispielsweise ein nichtleitendes keramisches Pulver, ein keramisches Substrat, ein metallisches Pulver oder ein metallisches Bauteil, insbesondere Al2O3, ZrO2 oder Pt, in Frage. Vor dem Einführen oder Eintauchen des Substrates kann das Substrat zusätzlich zuvor in an sich bekannter Weise aktiviert werden. Dies geschieht beispielsweise über eine Abscheidung eines Pd-Salzes an der Oberfläche.In the thus prepared rhodium bath, a substrate is now introduced or immersed, on which the rhodium contained in the bath is deposited electrolessly in metallic form. As a substrate to be metallized, for example, a non-conductive ceramic powder, a ceramic substrate, a metallic powder or a metallic component, in particular Al 2 O 3 , ZrO 2 or Pt, comes into question. Before the substrate is inserted or immersed, the substrate can additionally be activated beforehand in a manner known per se. This happens, for example, via a deposition of a Pd salt on the surface.
Nach dem Einführen oder Eintauchen des zu metallisierenden Substrates in das Rhodiumbad wird diesem als Reduktionsmittel weiter eine 10%-ige Hydrazinlösung zugetropft, die die Rhodiumabscheidung wesentlich beschleunigt.After introducing or immersing the substrate to be metallized in the rhodium bath this is further added dropwise as a reducing agent, a 10% hydrazine solution, which significantly accelerates the rhodium deposition.
Aus dem Rhodiumbad wurde dabei der weitaus größte Teil des enthaltenen Rhodiums in metallischer Form auf dem zu beschichtenden Substrat abgeschieden. Typische Badausbeuten liegen bei 90% und darüber. Der Abschluß des Abscheidevorganges durch Verbrauch des im Rhodiumbad enthaltenen Rhodiums ist in einfacher Weise an einer Entfärbung des Rhodiumbades erkennbar. Aufgrund der nahezu vollständigen Abscheidung des im Bad enthaltenen Rhodiums auf dem Substrat ist die in das Bad einzusetzende Rhodiummenge somit in einfacher Weise anhand der zu beschichtenden Oberfläche und der Dicke der zu erzielenden Beschichtung zu errechnen.From the rhodium bath, by far the largest part of the contained rhodium was deposited in metallic form on the substrate to be coated. Typical Badausbeuten are 90% and above. The conclusion of the deposition process by consumption of the rhodium contained in the rhodium is easily recognizable by a decolorization of the rhodium bath. Due to the almost complete deposition of rhodium contained in the bath on the substrate to be used in the bath rhodium is thus calculated in a simple manner based on the surface to be coated and the thickness of the coating to be achieved.
Claims (6)
- Rhodium bath, in particular for the electroless deposition of rhodium on substrates, the rhodium bath containing at least one rhodium compound which is readily soluble in water and water as solvent, characterized in that the rhodium compound which is readily soluble in water is ammonium-di(pyridine-2, 6-dicarboxylate)-rhodium(III) or a rhodium acetate, and in that the pH of the bath is between 8.5 and 10.5.
- Rhodium bath according to Claim 1, characterized in that a wetting agent, in particular a surfactant, such as a fluoroalcohol is added to the rhodium bath.
- Rhodium bath according to Claim 1, characterized in that the pH of the bath is between 9 and 10.
- Rhodium bath according to Claim 1, characterized in that from 1 to 50 g/l, in particular from 5 to 15 g/l, of rhodium can be dissolved in the rhodium bath.
- Process for depositing rhodium on a substrate using a rhodium bath according to at least one of Claims 1 to 4, characterized in that the end of coating of the substrate is indicated by the rhodium bath losing its colour.
- Use of a rhodium bath for the electroless deposition of rhodium on substrates, the rhodium bath containing at least one rhodium compound which is readily soluble in water and water as solvent, characterized in that the rhodium compound which is readily soluble in water is ammonium-di(pyridine-2, 6-dicarboxylate)-rhodium(III) or a rhodium acetate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1999109678 DE19909678C1 (en) | 1999-03-05 | 1999-03-05 | Rhodium plating bath useful for electroless plating of ceramics and metals comprises water and a readily water-soluble rhodium compound |
| DE19909678 | 1999-03-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1035229A1 EP1035229A1 (en) | 2000-09-13 |
| EP1035229B1 true EP1035229B1 (en) | 2006-09-13 |
Family
ID=7899803
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP20000103134 Expired - Lifetime EP1035229B1 (en) | 1999-03-05 | 2000-02-16 | Rhodium bath and process for rhodium deposition |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP1035229B1 (en) |
| JP (1) | JP2000282248A (en) |
| DE (2) | DE19909678C1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5081830B2 (en) | 2005-10-13 | 2012-11-28 | ヴェロシス インコーポレイテッド | Electroless plating in microchannels |
| CN110952081B (en) * | 2018-09-27 | 2022-04-29 | Imec 非营利协会 | Method and solution for forming interconnects |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1771053A1 (en) * | 1968-03-28 | 1971-11-25 | Telefunken Patent | Process for the electroless deposition of metal layers of the platinum metal group on surfaces of metallic and non-metallic parts |
| CH606475A5 (en) * | 1976-02-05 | 1978-10-31 | Bbc Brown Boveri & Cie | |
| US4402802A (en) * | 1981-01-03 | 1983-09-06 | Dequssa Aktiengesellschaft | Electrolytic bath for the deposition of rhodium coatings |
| JPS5939504B2 (en) * | 1982-05-19 | 1984-09-25 | 工業技術院長 | Electroless plating bath for rhodium or rhodium alloys |
| US4789437A (en) * | 1986-07-11 | 1988-12-06 | University Of Hong Kong | Pulse electroplating process |
-
1999
- 1999-03-05 DE DE1999109678 patent/DE19909678C1/en not_active Expired - Fee Related
-
2000
- 2000-02-16 EP EP20000103134 patent/EP1035229B1/en not_active Expired - Lifetime
- 2000-02-16 DE DE50013442T patent/DE50013442D1/en not_active Expired - Fee Related
- 2000-03-02 JP JP2000057560A patent/JP2000282248A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE50013442D1 (en) | 2006-10-26 |
| EP1035229A1 (en) | 2000-09-13 |
| JP2000282248A (en) | 2000-10-10 |
| DE19909678C1 (en) | 2000-07-27 |
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